EP0943595B1 - Procédé pour la séparation d'alcénes et d'alcanes - Google Patents

Procédé pour la séparation d'alcénes et d'alcanes Download PDF

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Publication number
EP0943595B1
EP0943595B1 EP99301319A EP99301319A EP0943595B1 EP 0943595 B1 EP0943595 B1 EP 0943595B1 EP 99301319 A EP99301319 A EP 99301319A EP 99301319 A EP99301319 A EP 99301319A EP 0943595 B1 EP0943595 B1 EP 0943595B1
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EP
European Patent Office
Prior art keywords
ions
alkene
adsorption
zeolite
gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP99301319A
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German (de)
English (en)
Other versions
EP0943595A1 (fr
Inventor
Martin Bülow
Chang J. Guo
Dongmin Shen
Frank R. Fitch
Arthur I. Shirley
Virginia A. Malik
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Linde LLC
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BOC Group Inc
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Publication of EP0943595A1 publication Critical patent/EP0943595A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S95/00—Gas separation: processes
    • Y10S95/90—Solid sorbent
    • Y10S95/902—Molecular sieve

Definitions

  • This invention relates to the separation of hydrocarbon gases, and more particularly to the separation of gaseous alkenes from alkanes by adsorption. Specifically, the invention relates to the separation of propene from propane or the separation of ethene from ethane by pressure swing adsorption (PSA) using a modified 4A zeolite adsorbent.
  • PSA pressure swing adsorption
  • alkenes e.g. propene
  • alkanes e.g. propane
  • the propene-propane mixture is fed into a C 3 -splitter, which typically is a 2-column distillation system.
  • the second column is substantially equal in size to the first column.
  • the first column separates a substantial portion of the propane to produce a chemical or refinery grade propene of at least 90 volume percent purity, typically about 96 volume percent.
  • the second column improves the purity level to 99+ volume percent to obtain polymer grade propene.
  • the separation of propene from propane by distillation is both difficult and costly because the process requires two large columns and is very energy intensive.
  • US-A-4,917,711 describes the adsorption of an alkene from a mixture containing the alkene and an alkane using an adsorbent comprising a copper compound and a high surface area support such as silica gel or zeolite molecular sieves, such as 4A zeolite, 5A zeolite, type X zeolite or type Y zeolite.
  • Patent No. 150885 describes the separation of alkenes from alkanes using 4A zeolite which has some of its exchangeable cations replaced by calcium or magnesium ions.
  • US-A-5,365,011 describes the separation of alkenes having 2 to 6 carbon atoms from alkanes having 2 to 6 carbon atoms by pressure swing adsorption at temperatures in the range of about 50 to 200°C using 4A zeolite.
  • the 4A zeolite may have up to 25% of its exchangeable sodium ions replaced by other ions, including potassium ions, calcium ions, strontium ions, etc., provided that the presence of the other ions does not cause the 4A character of the adsorbent to change.
  • This invention provides new adsorbents which can efficiently and effectively separate selected alkenes from selected alkanes.
  • a method of separating an alkene selected from ethene, propene, normal buteness or mixtures of these from a gas mixture comprising said alkene and an alkane selected from ethane, propane, normal or branched chain butanes and mixtures of these by a pressure swing adsorption process comprising the steps:
  • the adsorption step i.e., step (a) is carried out at a pressure in the range of about 1 to about 120 bara, and step (b) is carried out at a pressure in the range of about 0.15 to about 5 bara.
  • step (a) is carried out at a pressure in the range of about 1 to about 25 bara and step (b) is carried out at a pressure in the range of about 0.2 to about 2 bara.
  • the method of the invention is particularly useful for the separation of the alkenes from alkanes when the alkene and the alkane being separated contain the same number of carbon atoms.
  • the method of the invention is especially useful for separating ethene from gas mixtures containing alkanes, especially gas mixtures containing ethane, and it can be effectively used to separate ethene from a gas mixture when the gas mixture contains only ethene and ethane.
  • step (a) comprises passing the gas mixture through the preferred zeolite of the first embodimejnt, i.e. type A zeolite having as its exchangeable cations, about 55 to about 80% sodium ions, about 20 to about 35% potassium ions and 0 to about 5% ions selected from said residual ions, and in a most preferred aspect of this preferred embodiment, step (a) comprises passing the gas mixture through type A zeolite whose exchangeable cations consist substantially of sodium and potassium ions.
  • the adsorbent may be at least partly regenerated by depressurising and preferably evacuating the adsorption zone. Additionally, or alternatively, the adsorbent can be at least partly regenerated by purging the adsorption zone with alkene-depleted gas.
  • the adsorption zone may be purged with alkene-enriched gas prior to step (b).
  • Step (b) may be at least partly carried out by purging the adsorption zone with alkene-depleted gas.
  • the adsorption zone may be at least partially repressurised with alkene-depleted gas after step (b).
  • Alkenes which can be separated by the process of the invention are the normal alkenes having 2 to 4 carbon atoms, which include ethene, propene, butene-1 and butene-2.
  • the process of the invention is applied to the separation of normal alkenes having 2 to 4 carbons from alkanes having 2 to 4 carbon atoms.
  • the most beneficial application of the invention involves the separation of a normal alkene having 2 to 4 carbon atoms from the corresponding alkane, i.e., an alkane having the same number of carbon atoms as the alkene being separated.
  • Preferred separations include ethene-ethane separation, propene-propane separation and the separation of one or more normal or branched chain butanes. The most preferred separation is ethene-ethane separation.
  • the process of the invention can be carried out in a system comprising a single adsorption unit or a battery of adsorption units operated in phase, or a plurality of adsorption units or batteries of adsorption units operated out of phase, whichever is desired.
  • a system comprising a single adsorption unit or a battery of units all of which are operated in phase
  • the adsorption step must be periodically stopped to permit regeneration of the adsorbent bed(s)
  • a plurality of adsorption units are employed in parallel and operated out of phase, one or more units can be in adsorption service adsorbing the desired gas component, while one or more other units are undergoing regeneration to desorb and collect the adsorbed gas component.
  • Operation of the adsorption systems of the invention is cyclical.
  • cycles are repeatedly carried out in an manner such that production of the desired product gas is substantially continuous.
  • the process is carried out in a system comprising multivessel adsorption systems with the vessels arranged in parallel and operated out of phase, such that one vessel is in the adsorption phase while another is in the adsorbent regeneration phase, with each vessel being packed with the novel adsorbent of the invention.
  • the steps of the PSA process used in carrying out the alkene-alkane separation are not critical to the invention.
  • the adsorption cycle includes, as basic steps, an adsorption vessel pressurisation step, a production (adsorption) step and an adsorption regeneration step.
  • the vessel pressurisation step the pressure in the adsorption vessel in which the adsorption process is carried out is raised to the desired adsorption pressure.
  • a gaseous alkene and alkane-containing feed is passed cocurrently through the adsorption vessel (in the direction from the feed inlet end towards the non-adsorbed product outlet) at the desired adsorption pressure.
  • an alkene-enriched component is adsorbed and an alkene-depleted non-adsorbed gas fraction passes out of the adsorption vessel.
  • the bed regeneration step is carried out by countercurrently (in the direction opposite the cocurrent direction) reducing the pressure in the adsorption vessel and/or evacuating the vessel with a vacuum pump or other evacuation means, thereby desorbing the alkene-enriched product gas from the vessel.
  • the PSA cycle used in the invention may include steps other than the basic steps described above.
  • the cycle may include one or more bed equalisation steps, a non-adsorbed product backfill step, a countercurrent non-adsorbed product purge step and a cocurrent desorbed product gas purge step at or below the desired adsorption pressure.
  • the cocurrent purge generally precedes the evacuation step, and is generally carried out after any cocurrent depressurisation steps, e.g. equalisation steps.
  • Countercurrent purge is generally carried out during or after countercurrent evacuation of the adsorption vessel.
  • the sequential order and duration of the various steps are not critical, and these may be varied, as desired.
  • the adsorbents used in the invention are sodium and potassium-exchanged type A adsorbents about 50 to 85% of whose exchangeable cation sites are occupied by sodium ions, about 15 to 40% of whose exchangeable cation sites are occupied by potassium ions and optionally up to about 10% of whose exchangeable cation sites are occupied by ions other than sodium and potassium ions. In preferred embodiments when ions other than sodium and potassium ions are present, they do not occupy more than about 5% of the total exchangeable cation sites.
  • Such other ions include Group IA ions other than sodium and potassium, e.g. lithium ions, Group IB ions, e.g. copper I ions, silver I ions, etc., Group IIA ions, e.g. calcium ions, magnesium ions, strontium ions, etc., Group IIIA ions, e.g. aluminium ions, Group IIIB ions, e.g. gallium ions, and ions of the lanthanide series of elements.
  • Preferred adsorbents are type A zeolites whose exchangeable cation sites are occupied substantially by sodium ions and potassium ions.
  • Preferred type A zeolites have substantially only sodium and potassium ions as exchangeable cations, and about 60 to 85% of their exchangeable cation sites are occupied by sodium ions and about 15 to about 40% of its sites are occupied by potassium ions, and most preferred adsorbents are type A zeolites having substantially only sodium and potassium ions as exchangeable cations and about 65 to 80% of whose sites are occupied by sodium ions and about 20 to 35% of whose sites are occupied by potassium ions.
  • the temperature at which the adsorption step of the PSA process is carried out depends upon a number of factors, such as the particular alkene and alkane being separated, the particular adsorbent being used and the pressure at which the adsorption step is carried out.
  • the adsorption step is carried out at a minimum temperature of about 50°C, and it is preferably carried out at a minimum temperature of about 70°C.
  • the upper temperature at which the adsorption step of the process is carried out is a matter of choice.
  • the adsorption step can be carried out at a temperature below the temperature at which the alkene being separated undergoes chemical reaction, e.g. oligomerisation or polymerisation.
  • the adsorption step of the process can be carried out at temperatures up to about 200°C, but in preferred embodiments the upper adsorption temperature does not exceed about 175°C, and in most preferred embodiments, it does not exceed about 160°C.
  • the pressures at which the adsorption and adsorbent regeneration steps are carried out are likewise a matter of choice, and in general, these steps can be carried out at any of the usual pressures employed for gas PSA processes.
  • the pressure at which the adsorption step is carried out is determined by economics.
  • the adsorption step is carried out at pressures in the range of about 0.5 to about 50 bara (bar absolute), and this step is preferably carried out at pressures in the range of about 1 to about 25 bara; and typically, the adsorbent regeneration step is carried out at pressures in the range of about 1.5 to about 5 bara and this step is preferably carried out at pressures in the range of about 0.2 to about 2 bara.
  • the adsorption step was carried out at a pressure of about 5 bara, the beds were equalised to a pressure of about 3 bara, and the beds were countercurrently depressurised to a pressure of about 1.3 bara.
  • a feed gas composed of about 50% ethene and about 50% ethane (by volume) was used as the feed gas.
  • the flow rate of the feed stream, high pressure product (HPP) and low pressure product (LPP), which are determined for standard conditions, i.e., room temperature and atmospheric pressure are reported in standard litres per minute (SLPM). The results are reported in the Table.
  • Adsorbent A is zeolite A substantially all of whose exchangeable cations are sodium ions; adsorbent B is zeolite A having as exchangeable cations 79.4% sodium ions and 20.6% potassium ions; and adsorbent C is zeolite A having as exchangeable cations 76.4% sodium ions and 23.7% potassium ions.
  • the reported temperatures are average temperatures in the vessels throughout the entire cycle.
  • Example 3 The procedure of Example 3 was repeated, except that the adsorption cycle step durations were: bed equalisation (4 secs), cocurrent pressurisation with feed gas (8 secs), cocurrent adsorption of the feed gas (108 secs), bed equalisation (2 secs) and countercurrent depressurisation (116 secs). The total time for a half-cycle was 120 secs. The results are reported in the Table.
  • Example 4 The procedure of Example 4 was repeated except that the feed gas comprised 77.5% ethene and 22.5% ethane and the adsorption cycle step durations were: bed equalisation (8 secs), cocurrent pressurisation with feed gas (8 secs), cocurrent adsorption of the feed gas (110 secs), bed equalisation (4 secs) and countercurrent depressurisation (116 secs). The total time for a half-cycle was 120 secs. The results are reported in the Table.
  • Example 1 is a comparative example and Examples 2-5 are within the scope of the invention.
  • a comparison of the results of the examples illustrates that partially potassium-exchanged zeolite A (Examples 2-5) provides significantly better ethene recovery and ethane rejection than does the base zeolite A, a substantially 100% sodium-exchanged zeolite (Example 1).

Claims (10)

  1. Procédé de séparation d'un alcène choisi parmi éthène, propène, butènes normaux ou mélanges de ceux-ci, d'avec un mélange de gaz comprenant ledit alcène et un alcane choisi parmi éthane, propane, butanes et mélanges de ceux-ci par un procédé d'adsorption à pression alternée, comprenant les étapes consistant à:
    (a) faire passer ledit mélange de gaz dans au moins une zone d'adsorption contenant une zéolithe de type A possédant, en guise de cations échangeables, de 50 environ à 85 % environ d'ions sodium, de 15 environ à 40 % environ d'ions potassium et de 0 à 10 % environ d'autres ions choisis parmi les ions du Groupe IA autres que le sodium et le potassium, les ions du Groupe IB, les ions du Groupe IIA, les ions du Groupe IIIA, les ions du Groupe IIIB, et les ions de la série des lanthanides, adsorbant ainsi au moins une partie dudit alcène dudit mélange de gaz et produisant un gaz appauvri en alcène ; et
    (b) régénérer ladite zéolithe, produisant ainsi un gaz enrichi en alcène.
  2. Procédé selon la Revendication 1, dans lequel ladite zéolithe possède, en guise de cations échangeables, de 55 environ à 80 % d'ions sodium, de 20 environ à 35 % environ d'ions potassium et de 0 à 5 % environ d'ions choisis parmi lesdits ions résiduels.
  3. Procédé selon la Revendication 1 ou la Revendication 2, dans lequel les cations échangeables de ladite zéolithe sont constitués d'ions sodium et potassium.
  4. Procédé selon la Revendication 1 ou la Revendication 2, dans lequel lesdits ions résiduels sont choisis parmi les ions cuivre(I), les ions lithium, les ions calcium, les ions magnésium, les ions strontium, les ions aluminium et les ions gallium.
  5. Procédé selon l'une quelconque des Revendications précédentes, dans lequel l'étape (a) est réalisée à une température d'au moins 50°C.
  6. Procédé selon la Revendication 5, dans lequel l'étape (a) est réalisée à une température comprise dans une plage de 50°C environ à 200°C environ.
  7. Procédé selon l'une quelconque des Revendications précédentes, dans lequel ledit alcène et ledit alcane contiennent le même nombre d'atomes de carbone.
  8. Procédé selon l'une quelconque des Revendications précédentes, dans lequel l'étape (b) englobe la purge de ladite zone d'adsorption avec le gaz appauvri en alcène.
  9. Procédé selon l'une quelconque des Revendications précédentes, comprenant de plus la purge de ladite zone d'adsorption avec le gaz enrichi en alcène avant l'étape (b).
  10. Procédé selon l'une quelconque des Revendications précédentes, comprenant de plus la remise sous pression, au moins partiellement, de ladite zone d'adsorption avec le gaz appauvri en alcène après l'étape (b).
EP99301319A 1998-03-18 1999-02-23 Procédé pour la séparation d'alcénes et d'alcanes Expired - Lifetime EP0943595B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US4057498A 1998-03-18 1998-03-18
US40574 1998-03-18

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EP0943595B1 true EP0943595B1 (fr) 2002-01-16

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US (1) US6200366B1 (fr)
EP (1) EP0943595B1 (fr)
DE (1) DE69900656T2 (fr)
ES (1) ES2166632T3 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7148392B2 (en) 2003-06-17 2006-12-12 Exxonmobil Research And Engineering Company Separation of 1-butene from C4 feed streams

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US6488741B2 (en) * 2001-01-23 2002-12-03 The Trustess Of The University Of Pennsylvania Light hydrocarbon separation using 8-member ring zeolites
US6517611B1 (en) * 2001-07-23 2003-02-11 Engelhard Corporation Olefin separations employing CTS molecular sieves
US6576043B2 (en) * 2001-10-12 2003-06-10 Air Products And Chemicals, Inc. Recovery of nitrogen and light hydrocarbons from polyalkene purge gas
US6730142B2 (en) 2002-03-19 2004-05-04 Exxonmobil Research And Engineering Company Separation of propylene from hydrocarbon mixtures
US6733572B2 (en) 2002-07-30 2004-05-11 Exxonmobil Chemical Patents Inc. Separation of propylene and dimethylether from hydrocarbon mixtures
US6984765B2 (en) 2003-09-08 2006-01-10 Exxonmobil Chemical Patents Inc. Separation of methanol, ethanol and/or dimethyl ether from hydrocarbon mixtures
US7332640B2 (en) * 2003-10-31 2008-02-19 Exxonmobile Research And Engineering Company Light hydrocarbon separation using 8-member ring zeolites
ES2249183B1 (es) * 2004-09-15 2007-12-01 Universidad Politecnica De Valencia Uso de material cristalino microporoso de naturaleza zeolitica con estructura lta (itq-29) en procesos de adsorcion y separacion de compuestos organicos.
ES2275422B1 (es) * 2005-07-25 2008-06-01 Universidad Politecnica De Valencia Separacion de gases utilizando la zeolita itq-32.
KR100822847B1 (ko) * 2007-03-29 2008-04-16 한국에너지기술연구원 올레핀/파라핀 혼합가스에서 올레핀 분리 기술
KR100836707B1 (ko) * 2007-04-25 2008-06-10 한국에너지기술연구원 올레핀/파라핀 혼합가스에서 고순도 부텐-1 분리 기술
CA2618267C (fr) * 2008-01-21 2016-04-05 The Governors Of The University Of Alberta Zeolithes ets-10 pour la separation des olefines
WO2015031366A1 (fr) 2013-08-30 2015-03-05 Exxonmobil Chemical Patents Inc. Stockage d'oxygène et conversion catalytique d'alcanes
US9108891B1 (en) * 2014-11-21 2015-08-18 Chevron Phillips Chemical Company Ethylene separation with pressure swing adsorption

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Also Published As

Publication number Publication date
DE69900656D1 (de) 2002-02-21
US6200366B1 (en) 2001-03-13
DE69900656T2 (de) 2002-08-14
ES2166632T3 (es) 2002-04-16
EP0943595A1 (fr) 1999-09-22

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